Explosive



March 8, 1938.

1. w. D. HACKH ET AL EXPLOSIVE Filed Sept. 17, 1934 FIG. 4. m V

INVENTOR. INGO W. D- Hnckh BY JAMES D. McLsoo ATTORNEYS.

Patented Mar. 8,1938

UNITED} STAT-as PATENT OFF-ice axrrlosrva n' w. n. Hackh. San and James 1 McLeod, Oakland; Calif.

. mutation September 17,1984,8 erla1No. 744,962

7 Clalma This invention relates to explosives such as the ultra-compound explosives, and has for its objects an improved explosive and method of making the'same, which explosive is more economical and safer to make and handle and more efiective in'use' than explosives heretofore. Other objects and advantages will appear in the following description:

In the drawing'attachedhereto Figs. 1 to 5 are m diagrammatic representations of molecular structureto which reference will be made in the specification.

Broadly, our invention relates to the production of a nitro-compound explosive from a basic 5 mixture of nitro-compounds of the single benzene ring such as trinitrobenzene and/or its derivatives such as trinitrotoluen, picric acid,,styphnic acid, 1.3.5 trinitro-2-4-dimethyl benzene with the addition of suificient alkali, ammonium, or alkali go earth nitrate .to produce complete combustion.'

Other oxidizers may be used. In basic mixtures of the foregoing type, as is well known in the art, a very small amount of moisture, such as water, is present.

We have found that the foregoing basic explosive mixture is rendered highly explosive by the addition of a promoter or accelerating catalyst oi specified molecular structure and a catalytic explosive such as the nitronaphthalenes' or their derivatives, namely, a-mononitronaphthalene, fl-mononitronaphthalene, (1.2) (1.3) (1.4)

;5 cording to modern X-ray investigations and calculated from the recently published results by Linus Pauling and M. L. Huggins (Zeitschrift fur Kristallographic, vol. 87, page 205, 1934, publishedlby Akademische-Verlagsgesellschaft M. B-

50 H.'," Leipzig) and from the findings of E. H. Westling published in Chemical News (London) July 17;"1931. I

Referring to Fig. 1, the essential atomic dis- 35 tances in the naphthalene complex are:

Distance Angstrom units a": 7 3.83 b- "I4.19 j 4.84

- We haveviound that such molecules as come near to the above distances in theiressential atomic distance between the end atoms of their respective molecules, exclusive of hydrogen atoms,

are very eificieht'promoters in a powder mixture containing hum-derivatives of naphthalene.

nine, iso-butyric acid, a-chloropropionic acid, etc.,

or propanol or its alpha derivatives such as 1.1- dimethyl propanol, iso-butyl alcohol, etc., or its beta derivatives such as 2-methyl propanol, 2.2 dimethyl propanol, etc., or allyl alcohol and others; all have a distance within .09 angstrom units of being 3.83 angstrom units between their end atoms, and when any of these ingredients are addedto a suitable explosive mixture containing nitr'onaphthalenes it produces a very good brisance. and great shattering power.

Similarly we have found that 1.2-dichloroethane, ethylene chlorhydrlne, ,and trans-d1 chloroethylene and others have atomic distances close to 4.19 angstrom units and act as good promoters in setting ofi a mixture containing nitronaphthalenes.

Butanol and its alpha derivatives such as 1- methyl butanol, 1.1-dimethyl butanol or beta derivatives such as 2-methyl butanol, 2.2 dimethyl butanol, or its gamma derivatives such'as 3- methyl butanol, 3.3 dimethyl butanol, or its alpha and gamma derivatives such as 1.1.3.3-tetramethyl butanol or its alpha-beta-gamma deriva- 'tives such as 1.2.3-trimethyl butanol, or butyric acid or its alpha derivatives such as l-hydroxy butyric acid, l-methyl butyric acid, l-ammo butyric acid, or its beta derivatives such as 2- hydroxy butyric acid, Z-methyl butyric acid or butyric aldehyde or its alpha derivatives such as l-methyl butyric aldehyde, or its beta derivatives such as 2-methyl butyric aldehyde propane-1.3- diol, glycerol, methoxyethanol, ethyl acetate, methyl p'ropionate, act as good promoters in setting off an explosive mixture containing nitronaphthalenes since they have atomic distances close to 4.84 angstrom units. The molecular length of butyric aldehyde is closest to 4.84 angstrom units, hence is the most effective of "the compounds named.

Similarly, benzyl' alcohol or its derivatives such as o-hydroxy benzyl alcohol, m-hydroxy.benzyl alcohol, v-dihydroxy benzyl' alcohol, o-methyl benzyl alcohol, m-methyl benzyl alcohol or benzaldehyde or its derivatives such as o-hydroxytoluene come close to 5:13 in their molecular lengths, hence are good promoters in an explosive mixture containing nitronaphthalenes. Of the foregoing,-benzoic acid has a slowerebrisance than benzaldehyde, their respective molecular lengths being 5.18 and 5.11 angstrom units, which are within the limits of the atomic distances which act catalytically on the naphthalene complex.

We have tried many other substances, each ap-- proaching in its molecule one of the four essential atomic distances 3.83; 4.19; 4.84; or 5.13 angstrom units, and we find that the catalytic action will best occur if the effective distance occurs only at one place or direction in the molecule of the promoter. 'I'hus phthalic acid or phthalic aldehyde have the distance 5.18 or 5.11 in two directions, at an angle between the directions such that the average distance becomes quite diflerent to 5.18 or 5.11, the efiective distance of benzoic acid and therefore phthalic acid or phthalic aldehyde is less efiicient as a promoter than benzoic acid or benzaldehyde, for the tendency of the molecules to collide sideways prevents either of the useful distance 5.18 in phthalic acid or either of the useful distance 5.11 in phthalic aldehyde, to be effective.

The reason for nitronaphthalene molecules to decompose rapidly in the presence of a-promoter is the tendency of the naphthalene ring to break between the carbon atoms l and 2, and the carbon atoms 4 and B as shown diagrammatically in Figure 3 of the attached drawing (Figs. 2 to 5 inclusive showing the four possible ring fractures).

Of the four possibilities shown in Figs. 2 to 5, inclusive, III and V are identical and form a benzyl radical B as well as, a propyl radical P according to the equation:

where Col-14C" is the skeleton of benzaldehyde, B, and CaHa" an easily oxidized propionic residue P, while N02 is an active oxidizing group. Thus in the presence of either B or P the naphthalene ring is broken into B and 1. these decomposition products reacting again with the naphthalene ring to produce B and P. As long as molecules containing the naphthalene ring are present, this process will go on as a geometrically progressive chain reaction of the type: B or P (in the presence of the naphthalene ring) 2,110,220 benzaldehyde, m-hydroxy benzaldehyde. v-di- Therefore, a promoter containing the useful atomic distance of about 3.83, 4.19, 4.84, or 5.18 angstrom units will first decompose the nitronaphthalene, then the residual compounds of nitronaphthalene will partly act as catalysts to 5 the nitrobenzene compounds in the explosive mixture, and will partly act as promoters in breaking down more naphthalene rings and partly oxidize themselves and aid in the explosion, thus behaving as a catalytic explosive by taking an integral 10 part in the catalysis of the reaction as well asin the combustion.

While both benzaldehyde residues and propionic residues are formed from the naphthalene ring, and .while .also phthalic residues and .15 ethyl radicals may be formed in the splitting of the ring, and while all these may act as catalysts during the explosion, we flnd that for the initial splitting of the naphthalene ring any compound of the specified molecular length can act as a promoter. In general, the relativeamounts, by weight, of the promoter we add to the nitro naphthalene may be from 0.2 to 4%. v

The general formula (by weight) for our explosive mixture is thus: 1

0.005 to 2% promoter of approximate molecular length such as specified. I 5 to 10% catalytic explasive, such as nitronaphthalene derivatives. 15 to 55% explosive, such as trinltrobenzene and its derivatives. 40 to oxidizer, such as the alkali nitrates which include ammonium nitrate.

Per cent Alpha or beta-nitronaphthalene 7.5- 1.5-dinitronaphthalene 0.4 Normal butanol 0.1 'lrinitro benzene -1- 83 Sodium nitrate 59 g The above proportions are by weight, and the resultant mixture will decompose completely and 1' produces only a white smoke and no nitrous gases...

Another good explosive mixture is: w j

1 Per cent.

Alpha-nitronaphthalene "1.15 1.8-dinitronaphthalene .45 Propionic acid.. .08 1.3.5-trinitrotoluene 31.4 Sodium nitrate 60.92

This mixture explodes with a high brisance and leaves on explosion a white smoke and no nitrous A still further formula is: i

' Per cent Beta-nitronaphthalene 7.5

1.5-dinitronaphthalene 0.5 1 Benzaldehyde 0.08 Picric a i 88.12 Sodium nitrate 58.8

This mixture also explodes with a high brisance and leaves a white smoke and no objectionable gases.

We do not wish to limit ourselves to these three formulas. They merely indicate the use of trinitrobenzene,.trinitrotoluene and picric acid. We find that the promoters can be interchanged. Thus butanol can be used in all three mixtures.

Likewise a mixture of promoters can be used. As

ing a nitro-derivative of naphthalene, an oxidizer,

an organic promoter in an amount not greater than 2% by weight of the entire mixture,- said promoter being one of the compounds of a group in which the atomic distance between the opposite end atoms most remote from each other in each molecule therein exclusive of hydrogen is within .09 angstrom units of being equal to one of the four characteristic atomic distances of the naphthalene ringcomplex, namely 3.83; 4.19; 4.84; 5.13 angstrom units. 2. A nitro-compound explosive. mixture comprising a member 01' the group consisting of mononitro -naphthalene, dinitro-naphthalene, trinitro-naphthalene,, tetranitro-naphthalene, an oxidizer, and an organic promoter in an amount not greater than 2% by weight of the entire mixture, said promoter being one of the compounds oi a group in which the atomic distance between the opposite end atoms most remote from each other in each molecule therein exclusive of hydrogen is within .09 angstrom units of being equal to one of the four characteristic atomic distances of the naphthalene ring complex, namely 3.83; 4.19 4.84; 5.13 angstrom units.

3. A nitro-compound explosive mixture including a nitro-derivative of naphthalene, an oxidizer, and an organicpromoter in an amount not greater than- 2% by weight of the entire mixture, said promoter being one in which the atomic distance'between the opposite end atoms most'remote fromeach other in each molecule therein exclusive of hydrogen is within .09 angstrom units of being equal to one of the four characteristic atomic distances of the naphthalene ring complex, said promoter comprising a member of the group consisting of propanol, butanol, propionic acid, lactic acid, butyric acid, alanine, butyric aldehyde, benzaldehyde, benzoic acid and salicylic acid.

4. A nitro-compound explosive mixture including a nitro-derivative of naphthalene, an oxidizer, and a promoter, said promoter being benzaldehyde in an amount not greater than 2% by weight of the entire mixture.

5. A nitro-compound explosive mixture ineluding a nitro-derivative of naphthalene, an

being one of idle compounds of a group in which the-atomic distance between the. opposite end atoms in each molecule therein measured in the direction of the greatest length of the molecule, exclusive of hydrogen, is within .09 angstrom units of being equal to one of the tour characteristic atomic distances of the naphthalene ring complex, namely 3.83; 4.19; 4.84; 5.13 angstrom units.

INGO W. D. HACKH.

JAMES D.-'MCLEOD. 

